Halomethyl aliphatic amino compounds and processes of making them



Patented Sept. 22, 1942 QOUNDS AND THEM PROCESSES OF MAKING Edgar Wolf, Krei'eld, Germany, assignor to Heberlein Patent Corporation, New York, N. Y., a corporation of New York No Drawing. Application June 1'7, 1939, Serial 7 Claims.

In Germany December 4, 1936 I This invention relates to reaction products of amides and processes for making the same.

This application is a' continuation-in-part of my cope'nding application, Serial No, 177,054, filed November 29, 1937.

I have found in accordance with my invention I a series of new and useful products, being alphahalide derivatives of amides containing an'aiiphatic radical of at least ten carbon atoms, two mols of formaldehyde for each mol of amide and a hydrohalic acid. The said radical may be a naphthenic radical containing an aliphatic portion of 10 carbon atoms. The process and resulting products may employ, in addition, a substance wh-ich reacts to render the reaction product readily soluble in water. Substances which I prefer for this purpose are, for example, pyridine or other tertiary amine, forming a watersoluble quaternary ammonium compound with the amide-formaldehyde-halogen compound. The said products are particularly useful, for instance, in producing water-repellence in textiles and other materials, as stated in said abovementioned application, but their use is not restricted thereto. The expression formaldehyde, as used in this specification and in the appended claims, is intended to include not only formaldehyde, but also its polymers and substances splitting ofi formaldehyde under the reaction conditions of the process.

The principal objects of the present invention, accordingly, are to provide a series of useful compounds of the type mentioned and to produce simple, efficient processes for the manufacture of such compounds.

The invention, accordingly, consists in the novel products as well as the novel processes and steps of processes according to which such products are manufactured, the specific embodiments of which are described hereinafter by way of ex ample and in accordance with whichI now-prefer to practice the invention.

Substances which I have successfullymade in accordance with my invention' include the following:

The reaction product of stearic acid amide, trioxymethylene, and dry hydrochloric acid gas.

The reaction product of stearic acid amide, triamide,- trioxymethylene, and dry hydrochloric acid gas, rendered water-soluble by Pyridine.

The reaction product of stearic acid methylol amide, trioxymethylene and dry hydrochloric acid gas.

The reaction product of bicyclic naphthenic acid amide, trioxymethylene and dry hydrochlorio acid gas.

The above products, combined with pyridine, are readily soluble in water. are readily soluble in a non-aqueous solvent, such as benzine, for example. Combinationfivith pyridine or similar material with any of the substances of the above list will render them watersoluble.

Those uncombined It is known to prepare condensation products by reaction of fatty acid amides with aldehydes in the presence of acids or salts having an acid reaction, as for example, as set forth in French Patent No, 792,589. However, the products ob-' tained by this process are insoluble in water and cannot be brought into water-soluble form, even with the aid of tertiary amines. The melting point of the finished compounds lies substantially higher than that of the fatty acid amide which is employed. Furthermore, the condensation products which are obtained are difficult to dissolve or insoluble in organic solvents.

' I have discovered, in accordance with my inucts prepared by the process of the'said French patent, themethyl-halide derivatives produced in accordance, with my invention have a, melting point which is generally still substantially below that of the starting material. These methylhalide derivatives, and in particular their quaternary ammonium compounds, are easily.

soluble in various solvents.

In place of the fatty acid amides given, as above indicated the methylol compounds of the fatty acid amides may also be employed. Instead of fatty acid amides, as above stat'ed, I may employ naphthenic acid amides, but in either group only such amides are to be employed as have a saturated alkyl radical of at least 10 carbon atoms.

isnot to be considered as restricted thereto, ex-

cept as indicated in the appended claims.

a soluble product.

chloride compound takes place.

treated as stated in Example "1 and is stirred Examples 1. Into a mixture, at atemperature of about 40 0. F.), of 284 grams of stearic acid amide, 1500 grams of benzine, and 60 grams of trioxymethylene, dry hydrochloric acid gas is introduced until the formation of the methyl chloride compound takes place, which is recognizable purely externally by the clearing-up of the benzine'solution. The reaction water collected at the bottom of the vesselis drained off, the benzine and theexcesshydrochloric acid are driven off in a vacuum, and the methyl chloride compound obtained. It has a melting point of about 55 C. (131 F.). obtained may be used as such or may be combined with a tertiary amine to produce a water- For this purpose, it is stirred with 90 grams of pyridine at about, 100 C, whereupon the pyridine compound is formed, which is soluble in water.

Q. Into a mixture, at a temperature of 45 C. (113 F.), of 422, grams of montanic acid amide,

.2000 grams of benzine, and 60 grams of trioxymethylene, dry hydrochloric acid gas is introduced until the formation of the methyl chloride compound takes place. The latter is treated as stated'in Example 1 and is stirred with 90 grams of pyl'idine.

3. Into a mixture, at a temperature of 45 C. (113 F.) of 314 grams of stearic, acid methylol amide, 1500 grams of benzine, and grams of trioxymethylene, .dry hydrochloric acid gas is introduced until the formation of the methyl The latter is with 90 grams of pyridine.

4. Into'. a mixture, at a temperature of about C. (104 F.), of 284 grams of stearic acid amide, 1500 grams of benzine, and '60 grams of trioxymethylene, chlorine gas is introduced until the formation of the methyl chloride compound takes place, which is recognizable purely externally by the clearing-up of the benzine solution. The reaction water collected at the bottom of the-vessel is drained off, the benzine and the excess chlorine are driven off, in a vacuum, and the methyl chloride compound obtained. It has a melting point of about C. (131 F.). The product so obtained may be used as such or may be combined with a tertiary amine to produce a water-soluble product. For this purpose, it is stirred with 90 grams of pyridine at about 100 C., whereupon the pyridine compound is formed which is soluble in water. J,

5. Into a mixture, ata temperature of about 40 C. (104 F.), 1500 grams of benzine, and 260 The product so off in a vacuum, and the methyl chloride compound obtained. It has a melting point of about 55 C. The latter is treated as stated in Example land is stirred with 90 grams of pyridine.

It will be noted that in the examples above,

' employing trioxymethylene, except Example 3 that an amount of trioxymethylene is employedequal to two mols of formaldehyde for each mol j of amide used. In the case of Example 3, stearic acid methylol amide is treated which already contains one mol of formaldehyde, and then a second mol of formaldehyde is introduced in the I form of trioxymethylene.

or scope of the invention, and it is intended in the appended claims to cover all such changesand modifications.

What is claimed as new and desired to be se-' cured by Letters Patent is:

1. The reaction product of a fatty acidamide containing an aliphatic radical of at least ten carbon atoms, 2 mols of formaldehyde for each mol of fatty acid amide, and hydrochloric acid,

said reaction product being then combined with a tertiary amine.

2. A process which comprises bringing, together under reaction conditions a fatty acid amide having an aliphatic radical of at least ten carbon atoms, formaldehyde, and a hydrohalic acid, .there being present two mols of formaldehyde for each mol of amide, and combining with the reaction product resulting therefrom a tertiary amine.

3. A process which comprises bringing together under reaction conditions a fatty acid methylol amide having an aliphatic radical of at least ten carbon atoms, one mol of formaldehyde for each mol of methylol amide and a hydrohalic acid and combining with thereaction product resulting therefrom a tertiary amine.

' 4. The reaction product of stearic acid methylol amide, one mol of formaldehyde for each mol of methylol amide, and a hydrohalic acid thereafter reacted with pyridine.

. 5. The reaction product of montanic acid amide, two mols of formaldehyde for each niol of said acid amide, and hydrochloric acid thereafter reacted with pyridine.

grams of bicyclic naphthenic acid amide of high molecular weight, and 60 grams of trioxymethylene, dry hydrochloric acid gas is introduced until theformation of the methyl chloride compound takes place, which is recognizable purely externally by the clearing-up of the banzine solution. The reaction water collected at the bottom of the vessel is drained-off, the benzine and the excess hydrochloric acid are driven 7. The reaction product of stearic acid amide,'

two mols of formaldehyde for each mol of said acid amide, and hydrochloric acidthereafter reacted with pyridine.

EDGAR. WOLF.- 

